TW200837043A - A process for enhancing the operability of hot gas cleanup for the production of synthesis gas from steam-hydrogasification producer gas - Google Patents
A process for enhancing the operability of hot gas cleanup for the production of synthesis gas from steam-hydrogasification producer gas Download PDFInfo
- Publication number
- TW200837043A TW200837043A TW096137959A TW96137959A TW200837043A TW 200837043 A TW200837043 A TW 200837043A TW 096137959 A TW096137959 A TW 096137959A TW 96137959 A TW96137959 A TW 96137959A TW 200837043 A TW200837043 A TW 200837043A
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- TW
- Taiwan
- Prior art keywords
- synthesis gas
- gas stream
- gas
- methane
- stream
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/382—Multi-step processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
- C10K3/003—Reducing the tar content
- C10K3/005—Reducing the tar content by partial oxidation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
- C10K3/003—Reducing the tar content
- C10K3/006—Reducing the tar content by steam reforming
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/84—Energy production
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/26—Fuel gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0966—Hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
- C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Processing Of Solid Wastes (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Industrial Gases (AREA)
Description
200837043 九、發明說明: 【發明所屬之技術領域】 ,的領域係_原料合成運輪燃料。 【先前技術】 由於受到包含環境、健康、 燃料供應將來不可避免的缺乏在内的以石油為主之 使,因而需要鑑別新的化學能來 p關,主㈣所羅 。王世界以内燃機供給燃料的交通工具數量持 ::長,特別是在開發中國家的中程。 在吳國境外主要使用柴油之全球兄内相比, 快。當引進使用混合及/或柴油丨擎 ^ p成長得更 六、s θ 5丨拏技術之更具燃料效率的 =工?以同時降低燃料消耗及總體排放時,這種情 獲侍改變。由於用於生產 鉍告π L 屋以石油為主之燃料的資源正逐漸 i,因此除非開發出非石油替 燒的合成柴油_尤其是潔淨燃 θ '”、彳對石油的依賴將成為主要的問 ===用主廢氣排放控制的嚴格方法,否則在傳 、、-汰、切、·々/為主之燃料的正常燃燒會引起嚴重的環境 2。>糸甲燃燒的合成柴油燃料可助於降低柴油引擎的排 產生潔淨燃燒的運輪燃料需要重製現有以石油為主之 新穎方:喬現-自ΐ利用過的材料來產生動力或合成燃料之 、矛、法彳許多來自可再生有機材料或廢棄石炭質材料的 Γ源可利用。利用破質廢棄物來生產合成燃料為經濟上可 丁勺方去’因為饋入的原料已被認定沒有多少價值,被當 94117 5 200837043 料) 作廢棄物丟棄,且處理時經常造成污染。或者,可使用煤 作為原料以將低等級骯髒的固體燃料升級為價值婵 : :乾淨的液體燃料(例如高品質、環保合成柴油或‘_ 液體運輸燃料相較於氣體燃料具有天生的優勢,液體 ,燃料在相同的壓力及温度時具有比氣體燃料更高的能 里岔度。液體燃料可儲存在大氣壓或低壓,然而為了達到 ,液體燃料的能量密度,氣體燃料則必須在高壓下儲存於交 具之儲槽中,這在滲漏或突然破裂的情況下可能會有 =全的顧慮。液體燃料的分配係使用簡單的幫浦和^輸 官’故比氣體燃料的分配更容易許多。現有運輸部門供應 液體燃料之基礎設施(infrastructure)將確保可輕易整合至 任何生產潔淨燃燒的合成液體運輸燃料的現有市場。 潔淨燃燒的液體運輸燃料的可取得性是國家優先考慮 的事。潔淨且有效地由碳寶來源產生合成氣體(氫與一氧: (碳的混。合物,亦稱為合成氣體),該等碳質來源可進行費歇 爾·托羅普希製程(Fischer_Tr〇psch pr〇cess)以產生潔淨且 有價值的合成汽油及柴油燃料,將同時對運輸部門及社會 的健康有益。此製程能將當今最先進的引擎廢氣後處理^ 應用於N〇x的減少、將存在於柴油引擎廢氣之有毒粒子移 :及將正$燃燒產物污染物減少,該製程目前是透過催化 劑完成,該催化劑會被任何存在的硫迅速毒化,像是普通 石/由何生的柴油燃料原料之情況,而降低該催化劑的效 率地由合成氣體所產生之費歇爾-托羅普希·液體燃 94117 6 200837043 料ί硫、無芳香族物質,且在合成柴油燃料的情況中具有 超咼十六貌值。 、,生貝(bl〇maSS)疋最普遍被處理的用於產生可再生燃 :之碳質廢棄物原料。廢棄塑膠、橡膠、肥料、作物殘餘 :、林業、樹木及草地㈣物及來自廢水(污水)處理之生 貝固體(b刪lid)亦為用於轉換製程之候選原料。生質原料 轉換以產生電、熱、有用的化學製品或燃料。美國加 …在—使用和發展數種生質利用技術方面是全國中最頂尖 以在☆加財超過45百萬嘴的都市111體廢棄物被丢棄 乂經由廢莱物管制設備處理。此廢棄物大約有-半被送到 :圾掩埋場。例如,僅在加州地區河濱郡(Riverside c_⑺ 2估計每天處理約4_嘲廢棄木材。根據其他評估,每 =超過!00,_嘴生質被傾倒在河濱郡收集區的垃圾掩 此都市廢棄物包括肖3G%廢紙或廢紙板、辦 =匆和食物)廢棄物、* 3G%木材、紙張、塑膠和金屬廣 :物之、组合。若可將其轉換成潔淨燃燒的燃料,則華 = 化學能’其㈣用於降低對其 :里來源的需求。這些碳質材料的廢棄物來源不是 2::。在許多現有碳質廢棄物材料(例如紙張)可 :續、再利用及再循環的同時,對其他材料而言, 二製造者將該廢棄物直接送達轉換設備,則將 * 付傾倒費。廢棄物管制局通常收取目前㈣3Q / :::費’以抵銷處理成本。因此,藉由將廢棄物運 奢莱物轉換至‘合成燃料」加工廠不僅能降低處理成本, 94117 7 200837043 由於降低的處理成本亦將使額外的廢棄物可被利用。 在燃木火爐裡燃燒木材是使用生質來產生熱能的巧如 實例。可惜的是,開放式燃燒生質廢棄物來獲得能量二 並非是利用熱值(calorific vaiue)之潔淨且有效率的方法了 現今,利用碳質廢棄物之許多新穎方法正被發現。例如, 有一種方法是產生合成液體運輸燃料,另一種方法則是 生高能氣體以轉換成電。 ^ 使用來自可再生生質來源的燃料實際上能減少溫室氣 體(例如二氧化碳)的淨累積,同時提供用於運輸的潔淨且 有效率的能量。從生質來源共同生產一一uetiQn)合成液 體燃料主要益處之-為能提供可儲存的運輸燃料同時減少 促成全球暖化之溫室氣體效應。將來,這些共同生產製程 可為能持續供應的可再生燃料經濟提供潔淨燃燒的燃料。 存在有許多製程將煤及其他碳質材料轉換成潔淨燃燒 的運輸燃料,但是該等製程傾向於太昂貴而不能與以石油 為主之燃料在市場上競爭,或者該等製程會產生揮發性燃 料,例如具有過高蒸氣壓值而無法用於高污染地區(例如南 加州空氣域)之甲醇及乙醇,以致於無法從潔淨空氣法規中 立法tm免。近期製程之實例為Hyn〇l甲醇製程 (HynolMethanol Process),該製程利用加氫氣化 (hydro-gasification)及蒸氣重組反應器使用固體碳質材料 及天然氣共進料來合成甲醇,且該製程在實驗室研究規模 试驗(bench_scale demonstration)中證實具有〉85%之碳轉 換效率。: 8 94117 200837043 更近年來,在本案發明人的實驗室中已發展產生合成 氣體的方法,其中,在水中之碳質材料粒子的漿料、及來 自内部來源的氳係在生成富含發生爐氣體的條件下饋入至 加氫氣化反應器。在生成合成氣體的條件下將其與蒸氣一 起饋入至蒸氣熱解重組器以。此方法詳細記述於Norbeck 等人之美國專利申請案序號10/503,435(公開號US 2005/0256212),發明名稱 “ Production Of Synthetic Transportation Fuels From Carbonaceous Material Using (Self-Sustained Hydro-Gasification” 。 在此處特別關注方法之另一版本中,係使用蒸氣加氫 氣化反應器(SHR),將該碳質材料在氫和蒸氣皆存在下同 時加熱以在單一步驟中進行蒸氣熱解及加氫氣化反應。此 方法詳細記述於Norbeck等人之美國專利申請案序號 10/911,348 (公開號 US 2005/0032920),發明名稱 “Steam Pyrolysis As A Process to Enhance The Hydro-Gasification ,of Carbonaceous Material ” 。美國專利申請案序號 10/503,435及10/911,348皆以引用方式併入本文中。 經過氣化產生合成氣體及自合成氣體產生液體燃料是 完全不同的方法。合成氣體是使用蒸氣曱烧重組器(SMR) 產生的,該重組器是廣泛使用於產生液體燃料及其他化學 製品用的合成氣體的反應器。在該SMR中所進行之反應 可寫出如下: CH4+H20—> CO+3H2 (1) 或 9 94117 200837043 CH4+2H20 — > C02+4H2 (2) 一氧化碳及氫是在SMR中使用蒸氣及甲烷作為進料 所產生。慣例上,在蒸氣生成器加熱處理水而產生所需的 蒸氣,及甲烷通常是以經壓縮的天然氣形式供應,或是藉 由來自化學製程或精鍊製程之輕分子量排氣流的形式= 應。 ’、 或者,產自SHR之產物氣體可用作為SMR之原料, 其係藉由以在處理壓力下操作且位在SHR及SMR間的熱 氣淨化單元先從來自SHR的產物蒸氣移除硫雜質而進 行。此完整方法記述於美國專利案申請號u/489,3〇8,該 專利案之全部内容以引用方式併入本文中。然而,高至= 重量%之蒸氣含量可能與將從蒸氣_加氫氣化方法獲得的 發生爐氣體碰撞。此大量的蒸氣可藉由將下列反應的平衡 朝反向移動而使熱氣淨化製程中所使用的金屬氧化物吸附 劑之硫捕獲能力降低: ^
MO+H2S < — > MS+H2O 其中’ MO及MS分別表示金屬氧化物及金屬硫化物。該 吸附劑之硫捕獲能力的降低接著導致:⑴較高濃度: Ηβ,因而導致對於習知用於甲烷之蒸氣重組的以鎳=主 之催化劑的不利影響,該催化劑已知在不可逆的方式中相 當易受硫污染物傷害;(ii)較高污染的含有Η』之合成氣 體,及(iii)由於催化劑更換及壓降(pressure d⑺p)減弱之^ 頻繁製程轉變而造成合成氣體較差的產量。 因此,由於需要吸附劑在大量蒸氣的不利條件下發生 94117 10 200837043 ΓΓ用金4氧化物吸附劑移除H2S變得相當嚴格, 」”方止用於甲烷蒸氣重組之催化劑的硫毒化之程 :b巾要有用以提m ·加氫氣化發生爐氣體之敎 氧牙化之可操作性的改良方法。 ”、、 f發明内容】 =明係提供用於提升蒸氣_加氫氣化發生爐氣體之 =的爾性的經改良經濟替代性方法。該方法係 猎由將衣程的順序改變為包括下列之順序而達成: —瘵氣·加氫氣化,· —甲烧之自發性熱重組; --透過凝結以移除蒸氣;及 —熱氣淨化。 氣㈣倾供料提❹生合絲體的熱 以生成舍入二生!"方法,其中’富含甲烷之氣體流在足 約750。^=、—乳化礙之合成氣體流之溫度(約55代至 除所广^力下自發性熱重組。使該合成氣體凝結並移 獲^ ^下^㈣她使吸附劑捕 成氣體流…實質^ 約挪c至約、使雜質從合成氣體流移除之溫度, 及加二It發生爐氣體流可自分離的蒸氣熱解反應器 Γ體應器產生,但較佳為,該富含甲烧之發生爐 較佳為,1=自舍性熱重組前由蒸氣-加氫氣化產生。又 w哉-加虱氣化、自發性熱重組、凝結及硫雜質 94117 11 200837043 移除之壓力係始終實質上相同,約為150psi至5〇〇psi。 碳質材料可包括都市廢棄物、生質、木材、煤、或天 然聚合物或合成聚合物。經由移除雜質階段所生成的合成 氣體可用作為製程熱(pr〇cess heat)之燃料及/或用於可生 成電之燃料引擎或氣體渦輪機。甲烷自發性熱重組較佺係 在藉以使產生的合成氣體之組成具有3 : 4的H2: c〇莫耳 比的條件下進行,且經由移除雜質階段所生成的合成氣體 係在藉以產生液體燃料的條件下饋入至費歇爾_托羅普希 f反應器。來自費歇爾-托羅普希反應之放熱(ex〇thermic “叫 可饋入至蒸氣-加氫氣化反應及/或曱烷自發性熱重組反 在另一具體實施例中,本發明係提供將碳質材料轉換 為合成氣體之裝置,該裝置包括··用於在足以生成富含甲 烷之氣體流的溫度和壓力下,在氫和蒸氣皆存在下同時加 熱碳質材料與液態水的蒸氣-加氫氣化反應器;用以生成富 I〗δ氫和氧化故之合成氣體流的甲烧自發性熱重組機構; 用於使該合成氣體凝結成凝結物,藉以使合成氣體實質上 不含水的機構;及用於自該不含水之合成氣體流移除硫雜 質之機構。 該裝置可包括用於接收經純化生成的合成氣體以產生 液體燃料的費歇爾-托羅普希型反應器。可提供用於將來自 費歇爾-托羅普希型反應的放熱轉移至該蒸氣_加氫氣化反 應為及/或甲烷自發性熱重組機構的機構。 為更完整瞭解本發明,現請參照下列說明並配合附圖。 94117 12 200837043 【實施方式】 加奇:提1、,良的方法流程,該,法程序可提升蒸氣_ 口風礼化鲞生爐氣體之熱氣淨化的可操作性。 的值之—Λ體實關係揭絲❹於產生合成氣體 勺傳、、先瘵氣-加氫氣化的方法流程,包括: 將[蒸氣.氣氣化卜[熱氣淨化]—[甲燒之蒸氣重組] 改成 [蒸氣-加氫氣化卜[曱烷之自發性熱重組卜[藉由凝結移 除蒸氣]一[熱氣淨化]。 該改良的方法流程可用於其中有分離的蒸氣熱解反肩 器及,氫氣化反應器、接著為自發性熱重組反應器的產生 合成氣體的製程中,該合成氣體係用料製程熱之燃料及 或1於可生成電的燃料引擎或氣體渦輪機中;或在實質上 '自才才式製程中用作為饋入費歇爾托羅普希型反應器的達 料,以產生液體石蠟燃料、循環水及顯熱(sensibleheat)。 +較佳為該改良的方法流程係與其中碳質材料係在氣和 蒸氣2存在下加熱以在單一步驟中進行蒸氣熱解及加氫氣 化的瘵氣加氫氣化反應器(SHR)併用。 為了知用該改良的方法,必須符合下列數個條件··⑴ 用於甲烷之自發性熱重組的催化劑應能夠在高硫環境中對 甲烧重、、且維持令人滿意的活性,及⑴)在熱氣淨化前之蒸氣 凝結的溫度在操作壓力下不應顯著地低於熱氣淨化的溫 度’以便能增加適度量的熱而使所得氣體流升至實質上熱 氣淨化的溫度。 ,… 13 94117 200837043 :較佳具體實施例中,改良方法之第 二生成的氫連同竣質原料和液態水-起饋入至shr?:: 畐含甲貌之發生择氣體推 斤付 斤從! 進入自發性熱重組反應器t。將妳 =的氧單獨饋入至該自發性熱重組反應量: 佳需為約15體積%至25體積0/〇。 乳s里車乂 在自發性熱重組反應器中,較㈣使用貴金 ^相較於詩Μ蒸氣重組之以料主_化劑,用於 :自發性熱重組的貴金屬催化劑已知具有較高的活性及 生以及再生性。因此,由蒸氣_加氫氣化產生的 ^甲烧之氣體可藉由自發性熱重組以提高的可操作性進 订重組:含有高濃度硫化氫之富含甲垸之氣體可在流程中 重組為合成氣體持續長時間,且所使用催化劑 體大氣中再生。可使用之貴金屬催化劑之實例; 邮仙㈣,s ATR_7B 及 Hald〇r T〇ps〇e,s rks 2_7 3 RKS-2P 〇 ^ 甲烷之自發性熱重組後,可在不顯著低於熱氣淨化溫 度之溫度中,藉由凝結而自製程中移除蒸氣。在28巴(bar) 刼作壓力之情況中,蒸氣在230°C凝結成水,然後可在饋 入熱氣淨化階段前將蒸氣自製程流(pr〇cess討咖瓜)移除。 猎由在熱氣淨化前移除蒸氣,用於該熱氣淨化階段之金屬 氧,物吸附劑的硫捕獲能力可被完全地利用;且再加熱該 熱氣淨化製程流所需之能量負載可降低至很大程度,因為 製程流之比熱由於蒸氣的移除而顯著降低。例如,藉由Zn〇 吸附劑的熱氣淨化之最適溫度大約300°C,因此,為了蒸 94117 14 200837043 氣凝結而冷卻至23CTC之製程流只需再加熱70°C。 移除蒸氣後,所得之合成氣體在約350°C及約400 psi 直接進行熱氣淨化製程,該熱氣淨化製程包含通過淨化濾 器(例如濾燭式濾器組合件(candle filter assembly))。其接 著使該氣體通過進入氣體淨化單元。存在於SHR產物氣體 (product gas)之硫雜質主要以硫化氫之形式存在,該硫雜 質係藉由使合成氣體通過在該氣體淨化單元中之金屬氧化 物吸附劑的填充床來移除,顆粒物質係自濾餅出口取出。 活性吸附劑包含,但不限於,Stid-Chemie,Louisville, Kentucky所販售之以Zn為主之氧化物,例如氧化鋅。多 孔金屬濾器組件可以適當形式及尺寸購自 Marietta, Georgia 之 Bekaert,例如 Bekpor® Porous Media,其係由 具有1微米(micro meter)孔徑之不錄鋼燒結濾器基質所製 成。這些吸附劑及濾器組件使壓降及氣體-固體質量傳遞限 制的影響被減至最小。在28巴之壓力中,以25CTC至400 °C範圍的溫度及高至2000/小時之空間速度用於SHR產物 氣體之去硫化作用。在氣體淨化單元中所用之吸附劑一旦 硫捕獲能力顯著地降低時,則可以新鮮的吸附劑替換。 一旦經氣體分離裝置分離氮以再循環至自發性熱重組 反應器,所得之合成氣體接著可用於產生燃料及製程熱, 或該合成氣體在可產生無硫、具超高十六烷值的類柴油 (diesel-like)燃料及有價值的石臘產物|程中饋入至費歇 爾-托羅普希型反應器。無硫的存在能實現排出低污染物及 粒子的柴油燃料。可產生有用的副產物,例如純水,其可 15 94117 200837043 再循環以產生饋至該製程的漿料進料。費歇爾_托羅普希反 應亦產生含有氫、CO、c〇2及一些輕質烴氣體之尾氣。氫 可自尾氣脫出並再循環至SHR或費歇爾·粍羅普希反應 器。任何小量之其他氣體例如C0及c〇2可予以除去(flared Off) 〇 參知弟1圖’其係顯示該方法之流程圖。大約41重量 %煤、52重量%1^20及7重量%112之混合物1〇在約75〇〇c 之溫度及約28·0巴之起始壓力導入至蒸氣熱解及加氫氣 化之反應器12。此反應產生Η215·3%(體積)、c〇 11%(體 積)、co21.0%(體積)、ch4 34.3%(體積)、h2〇 復3%(體積) 及HJ 1000ppm之混合物14,而灰燼(來自加氫氣化反應 的未反應殘留物)則定期自該反應容器之底部移除。
在下一階段,在約550t:及約28.0巴之起始壓力以混 合物14及含有氧17%及氮83%之混合物(以體積%計) 進行甲烧自發性熱重組18 ’得到含有h2 41.9%、CO 12.8%、C02 2·5%、CH4 1·8〇/〇、Η20 13.7%、馬 27.3%、及 Ηθ 550ppm之混合物20 (以體積%計)。混合物16對混合 物14之體積比為約0.41。 接著’將蒸氣在約230°C及約28.0巴之起始壓力中在 階段22藉由凝結移除。由蒸氣凝結所產生的水接著在熱氣 淨化階段26前自製程流移除,留下含有h2 48.6%、C〇 14.8%、C02 2·9%、Ch4 2·1%、N2 31.6%、及 h2S 640ppm 之混合物24 (以體積%計)。此混合物24進入熱氣淨化階 段26,其中係施用約3〇(rc之温度及約28 〇巴之起始壓力 16 94117 200837043 以產生含有 Η2 48·60/0、C〇 14·8%、C02 2·9%、CH4 2·10/〇、 A 31.6%、及HJ少於〇.lppm之去硫化氣體混合物28 (以 體積%計)。 雖然已詳細述明本發明及其優點,然應瞭解在不會悖 離如所附申請專利範圍所界定之發明精神及範疇的情況 下,在此可進行各種變更、取代及修改。此外,不意欲將 本申請案之㈣限於說明書中所述的方法及裝置的特定具 體實施例。該領域具通常技藝者從本發明之揭示内容將能 輕易瞭解,可根據本發明而湘現存或後續將發展出來的 方法及裝置’該等方法及裝置係實f上執行與本文所述之 對應具體實施例相同的功能或實質上達到相同結果。因 此,所附申請專利範圍意將該等方法及該等褒置之使用包 含在其範轉内。 【圖式簡單說明】 第1.圖為根據特定具體實施例之本發明方法的 圖 ° 【主要元件符號說明 10 、 14 、 16 、 20 、 24 12 混合物 18 22 26 28 蒸氣熱解及加氫氣化之反應器 甲烧自發性熱重組 蒸氣凝結階段 熱氣淨化階段 去硫化氣體混合物 94117 17
Claims (1)
- 200837043 十、申請專利範圍: 1. 一種用於產生合成氣體的熱氣淨化之 方法’包括: 可操作性的提升 提供富含甲烷之氣體流; 二足以生成富含氫及一氧化碳之合成氣體流的益 度及麼力下,自發性熱重組該富她之氣體流; 使該合成氣體凝結並移除所得之水;及 自所得合成氣體流移除硫雜質。 2. 如申請專利範圍帛1項之方法,其中,該從凝結產生的 合成氣體流係加熱至實質上該雜質從該合成氣體流移 除之溫度。 3. 如申請專利範圍第!項之方法,其中,該雜質係在約25〇 C至約400 c從該合成氣體流移除。 4. 如申請專利範圍第2項之方法’其中,該自發性熱溫度 係約550°C至約750°C。 ,申明專利|&圍第1項之方法,其中,該合成氣體流之 凝結係在實質上該雜質從該合成氣體流移除之壓力下 進行。 6·如申請專利範圍第!項之方法,其中,該f含曱烧之發 生爐氣體流係產生自蒸氣_加氫氣化。 7·如申請專利範圍第6項之方法,其中,該蒸氣_加氫氣 化自發性熱重組、凝結及雜質移除之壓力係始終實質 上相同。 •如申請專利範圍第7項之方法,其中,該實質上相同的 18 94117 200837043 壓力係在約150psi至5〇〇psi之範圍中。 9· tc範圍第1項之方法,其中,使該富含甲貌之 =釋的氧之氧含量係在約15體積%至25體散: 範lij中。 t 10.二申:青專侧以項之方法,其中,該甲燒自發性熱 、、且糸在藉以使產生的合&氣體之組成具彳3 · 4的 H2 · CO莫耳比的條件下進行。 η.Π請Γ範圍第1項之方法,其中,該富含甲院之發 ί爐氣體流可從分離的蒸氣熱解及加氫氣化反應器產 生。 王 13·ί2專利範圍第1項之方法,其中,經由該移除雜質 ι 斤生成的合成氣體可用作為製程熱之燃料及/或用 於可生成電之燃料引擎或氣體渦輪機。 14·如申請專利範圍第1項之方法,其中,經由該移除雜質 ρ白&所生成的合成氣體係在藉以產生液體燃料的條件 下饋入至費歇爾-托羅普希反應器。 15.如申請專㈣㈣14項之方法,其包括將來 托羅普希型反應的放熱轉移至蒸氣-加氯氣化反應及 甲燒自發性熱重組反應。 -種用於產生合成氣錢熱m之可鮮性的提升 94117 19 200837043 方法,包括: 提供富含甲烷之氣體流; 、將j田3甲烷之氣體在約550°C至約750°C及在足 以生成富含氫與一氡化碳之合成氣體流之壓力下,藉由 與經氮稀釋的氧及廡;隹&义 ^ ^ 虱反應進仃自务性熱重組,該經氮稀釋的 氧之氧合里係在約15體積%至約25體積%之範圍中; 使該合成氣體凝結並移除所得之水; "“加熱該從凝結產生的合成氣體至實質上該硫雜質 從該合成氣體流移除之溫度;及、 在約25(TC至約4GGt中,從所得合成氣體流移除 該雜質; 該蒸氣-加氫氣化、自發性熱重組、凝結及雜質移 除之麼力係始終實質上相同,在約150 psi至500 psi之 範圍中。 A 一種將碳質材料轉換為合成氣體之裝置,包括: 用於在足以生成畜含甲烧之氣體流的溫度和壓力 :在氫和瘵氣皆存在下同時加熱碳質材料與液態水的 条氣·加氳氣化反應器; 用以生成富含氫和一氧化碳之合成氣體流的甲烷 自發性熱重組機構; “用於使該合成氣體凝結成凝結物,藉以使合成氣體 員質上不含水的機構;及 用於自該不含水之合成氣體流移除硫雜質之機構。 从如申請專利範_ ί7項之裝置,包含料使該富/甲 94117 20 200837043 烷之氣體流蒙受經氮稀釋的氧流以進行甲烷自 重組的機構。 x … 19. 如申請專利範圍f 17項之裝置,包含用於從該不含水 之合成氣體流分離氮,接著再循環該氮至用於甲烷自發 性熱重組的機構之機構。 又 20. 如申請專利範圍帛17項之裝置,包含用於接收用於產 生液體燃料之機構所生成的合成氣體之費歇爾_托羅普 希型反應器。 2!.如申請專利範圍第20項之裝置,包含用於將來自費歇 爾-托羅普希型反應的放熱轉移至該蒸氣_加氫氣化反應 器及/或甲烷自發性熱重組機構的機構。 94117 21
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US11/635,333 US8349288B2 (en) | 2006-12-06 | 2006-12-06 | Process for enhancing the operability of hot gas cleanup for the production of synthesis gas from steam-hydrogasification producer gas |
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TW096137959A TW200837043A (en) | 2006-12-06 | 2007-10-11 | A process for enhancing the operability of hot gas cleanup for the production of synthesis gas from steam-hydrogasification producer gas |
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US (1) | US8349288B2 (zh) |
EP (1) | EP2091901A1 (zh) |
JP (1) | JP2010511772A (zh) |
CN (1) | CN101547880A (zh) |
AR (1) | AR064005A1 (zh) |
AU (1) | AU2007328406A1 (zh) |
BR (1) | BRPI0716702A2 (zh) |
CA (1) | CA2669287A1 (zh) |
MX (1) | MX2009006057A (zh) |
TW (1) | TW200837043A (zh) |
WO (1) | WO2008069860A1 (zh) |
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-
2006
- 2006-12-06 US US11/635,333 patent/US8349288B2/en not_active Expired - Fee Related
-
2007
- 2007-10-10 CA CA002669287A patent/CA2669287A1/en not_active Abandoned
- 2007-10-10 BR BRPI0716702-4A patent/BRPI0716702A2/pt not_active IP Right Cessation
- 2007-10-10 AU AU2007328406A patent/AU2007328406A1/en not_active Abandoned
- 2007-10-10 JP JP2009540224A patent/JP2010511772A/ja not_active Withdrawn
- 2007-10-10 EP EP07839406A patent/EP2091901A1/en not_active Withdrawn
- 2007-10-10 MX MX2009006057A patent/MX2009006057A/es unknown
- 2007-10-10 WO PCT/US2007/021594 patent/WO2008069860A1/en active Application Filing
- 2007-10-10 CN CNA2007800451466A patent/CN101547880A/zh active Pending
- 2007-10-11 TW TW096137959A patent/TW200837043A/zh unknown
- 2007-11-28 AR ARP070105275A patent/AR064005A1/es unknown
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WO2008069860A1 (en) | 2008-06-12 |
CA2669287A1 (en) | 2008-06-12 |
US20080139675A1 (en) | 2008-06-12 |
AU2007328406A1 (en) | 2008-06-12 |
EP2091901A1 (en) | 2009-08-26 |
JP2010511772A (ja) | 2010-04-15 |
US8349288B2 (en) | 2013-01-08 |
BRPI0716702A2 (pt) | 2015-05-26 |
CN101547880A (zh) | 2009-09-30 |
MX2009006057A (es) | 2009-06-16 |
AR064005A1 (es) | 2009-03-04 |
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